Oil-soluble resinous composition



Patented Dec. 28, 1943 UNI-TED STATES, PATENT, 'orr cs om-sowsna assmons comosmon Gaetano F. DAlelio, Pittsfield, Mass aulgnor to General Electric Company,

New York a, corporation of s V No Drawing. Application February 17, 1949,

., Serial No. 349,515

14 Claims.

The present invention relates broadly to the production of resinous compositions. It is concerned-more particularly with the preparation of oil-soluble resins'of thefgeneral class consisting of alkyd-modified phenolic resins. I

It has been known heretofore that oil-soluble I H resins can be producedby condensing formaldehyde or the like with certain ortho and parasubstituted phenols, forlexample phenols substituted in'the para position-by hydrocarbon radicals containing four to seven' or more carbon atoms. ,"I'h'e broad suggestion'also has been made that such oil-soluble resins may be modified by incorporating therewith? substantially neutral resinous bodies,i'specifically substantially neutral natural resinsapdlyhydric' alcohol-natural resin esters, esterification'productsof polycarboxyllc acids withjbothj monohydric. and polyhydric zoo- 44) grouping. The described (hereafter, for brevity, designated generally as an unsaturated alkyd resin) should have pronounced acidity, as evidenced by an acid number alcohols, andesterific'ation products ,of .polyhydric alcohols with 'monocarboxylic and polycarboxylic.acids. 7 It also hasbeen known heretofore that alkydmodlfied phenolic resins can be soprepared as to yield resinous compositions capable of being poured into'molds, thatis, cast, and cured therein under the influence" of heat to the insoluble, infusible state. Casting resins so made are de-i scribed, for-example, in Kienle and Schlingman of at least 40, but in no case should the acid number be higher than 210. Such definitely acid,

partial esterification products are not to be con- ,resins and acidic flexible alkyd resins) contain both alcoholic hydroxylgroupsand carboxylic groups.

Patent No. 2,025,538, which is assigned to the same assignee as the'present invention. In accordance with the Kienie and Bchlingman invention a flexible alkyd resin is used as an acid catalyst in promoting reaction between phenol and an aldehyde such as paraformaldehydea In the copending application of Edmond F. Fledler, Serial No. 204,620, filed April 27, 1938, now Patent I No. 2,233,406, and assigned to the same assig'nee as the present invention, is disclosed the tact that phenol alcohols may be caused to react'with -flexible alik yd resins having an acid number between 140 and 210 to give satisfactory casting resins. The .permanently flexible alkyd resins permitted the production of shock-resistant castings because ,of the intrinsic flexibility of the alkyd component. The cured,- cast resins obtained by both Fiedler and Kienle et a1. were insoluble in oils.

.The present invention is based on my discovery that new and valuable oil-soluble resinous compositions of particular utility in the production "Numerous advantages accrue from practicing my invention. For "example, films of coating compositions comprising these new resinous bodies dissolved in, or coreacted with fatty oils,

specifically: drying and semidrying oils, or with other resinous-bodies internally modified by such oils, are lighter in color, tougher, brighter and otherwise more generally suitable than are similar compositions comprising a phenolic resin or an alkyd resin" alone. Further, the process of producing these new oil-soluble resins requires no special equipment and the properties, particularly flexibility and drying characteristics, of .the products can be readily controlled to yield a resin best adapted for the particularservice application of the individual coating composition.

These improved properties of'the fatty oil-resin.

compositions are believed to accrue at least in part, by reason of the ester exchange that may take place between the ester. radicals of these new resins and the ester groupings of the fatty oil. In this way the solubility of the resin in the oil is enhanced beyond that due to the substituent group in the phenolic component. The phenolic componentalso appears to contribute so-called of coating compositions can be produced by efiecting reaction between (1) an acidic esterlflcation product of a polyhydric alcohol and polycarboxylic acid comprising essentially an alpha unsaturated alpha beta polycarboxylic acid and (2) an alkaline-catalyzed partial condensation product of an aliphatic aldehyde with an orthoor para-substituted phenol having two reactive positions in the aromatic nucleus and containing at least four carbon atoms in the substituent "oil reactivity to the oil, whereby the time required for bodying the oil and for drying the films of the resulting varnish are considerably shortened.

fled flexible alkyd resins are utilized are more limited, generally speaking, in their applications (for on'e reason because they tend to dry to a hard film somewhat more slowly) than similar compositions comprising .-'an" unsaturated alkydresin-modified phenolic resin. As is well known, unsaturated alkyd resins (even those wherein the alcohol component is dihydric and the acid comesteriflcation product I Coating compositions prepared from oil-soluble resins wherein the hereinafter-identl- .ponent is dicerboxylic)v are convertible by doublejalkylol phenols; j (phenol alcohols),

acti'on' iscarried out temperatureofthe' m'ess. V; V Illustrative examples o fg orthoand para-sub- Ortho and par'abond polymerization to an insoluble. infusible state. This polymerization characteristic appears to I be carried into thevintercondensation product oi the alhrd resinand the phenolic resin, thereby :ivinlcil solutionsof the finished resin somewhat better drying and bodying characteristics than those obtained with a flexible alkyd resin as the modifying reactant. "Hence I prefer to use anunsaturatedalkyd'resin as the alkyd of cost per unit component of my new -resinous compositions.

Depending mainly'upon the particular'reactants employed, the proportions thereof and the extent.

of. dehydration, thesenew resins vary from hard, brittle solidstd soft, somewhat tacky masses. Allv are characterized by-j their solubility in oils, specifically fatty oils. .z 1.

In carrying thepresent invention 'into efiect' 1 a substituted phenol oi thekind-hbove-mentioned I lscausedsto. react, preferably-under aque us conditions, with an aliphatic aldehyde,',speciflcally formaldehyde, .in. the presence of an alkaline cat- 'alyst to 'formfa liquid mass comprisins. mainly specifically methylol' phenols,

.or mixtures thereof. This reternperatures, L usuallyunderi reflux at; the boiling .stituted mono-phen ls containing; at. leastxfour carbonatoms in .the substituerit group andhaving two reactive positions in the ring are {the butyl phenols. the; butyl meta cresols, th'e 'amyl-l meta "cre'solathe he ryl phenols, the the octyl phenols, the .octyl hexyl m'eta cresols; meta cresols,' the ;phenyl phenols, the tolylphenols, the .xylenyl phenols, the phenyl phenolpropanes, the phenyl phenol butanes, the phenyl-phenol pentanes, the

' nuclearlylalkylated phenyl; phenol alkanes, thethe terpene 'phenols,.etc., or, in 40 coum'ar -phenols,

otphenolobtained by chemical-.-

V and parts-amyl phenols-ortho- V lndene phenols and orthoe l and. para-(l -phenethyl) phenols,; a specific example of the latter beinpsymmetrical para phenyl phenol ethane The para-substituted phenols'a're preferred to the" ortho-substituted bodies, since, other conditions};

at normal or at elevated precluded, for

.2 beconsidera'bly varied, but

temperature (20?; to "35;

' percentage:- of catalyst is assure results have been obtained by using 1 mol phenol to 1.2 to 2.2 mole formaldehyde. Moi ratios of aliphatic aldehyde to phenol above 3 to 1 are not example 4 or'5 mole of aldehyde but no particular advantages acparticularly from theviewpoint yield.

7 1 The alkaline catalyst employed advantageous- 1y is one which has no darkening efiect upon the resin. .Hydroxides of the alkaline-earth metals (calcium, strontium and barium) and hydroxides, carbonates, cyanidesand'borates of the alkali metals (lithium, sodium, potassium, rubidium and caesium) are examples of suitable catalysts.

,Aminonia and derivatives of ammonia, e. g., the primary. secondary and tertiary amines and to 1 mol phen crue therefrom imines, likewisemay be used if color is of secondary consideration; The amount, of catalyst may generally is about 0.5 1:05 per cent by-weight of the substituted phenol.

The nearer there'action temperature approaches,

100 -C.,' the less catalyst is required. For room Qlreactions, a higher required as compared with reactions carried out underapplied heat,

and in suchicases may approach 10 per cent by weight of the phe'nolic body. At reaction temderivatives peratures of 'approi'rimately 80f to 90 C. an amount. of catalyst rangingff rom about 0.5 to 3.5 per cent by weight of the substituted phenol is efiective."

The substituted phenol and aliphatic aldehyde, e. fg.', formaldehyde, are intimately associated, for example by mixing and heating. for a, period suilicient to form alkylol, specifically methylol,

offlthe s'ubstitued phenol but insuflicient to cause the' conversion of all of such dev thelmethylene state. As is well known,.when I acted Junder alkaline conditions, phenol alcohols (alkylol phenols) are formed. Thus when the aldehyde 'is, for examplegforinaldehyde, as the reactionproceedsa higher condensation product forms with the acidicgflexible-alkyd resin, oran acidic unsaturated 'alkyd resin, not exceeding substantially 210 the same, thepara compounds yield resi'n'sfi having somewhat better oil. ticularly, greater light stability. v The'choice of the aliphatic aldehyde component is dependent largely upon economic considerationsiand upon the particular properties desired solubility and, peraldehydic componentrformaldehyde or polymeric modifications thereof such'as the'polyoxymethylenes, e. 3., paraformaldehyde, 'trioxymethylene', etc. For some applications ofthe finished resin '1 may use other'aliphatic aldehydes, for example,

acrolein, acetaldehyde, propionaldehyde, butyraldehyde, crotonaldehyde, etc., mixtures thereof or 'mixtures of formaldehyde (or compounds ene 110.2%; or 3 mols. aliphatioaldehyde. Very good .inthe finishedproduct. I prefer to use as .the

. mass} comprising. mainly; alkylol, I specifically 1 the, {above substituted 55 when dehydrated, are" in acidi'nurnbii is; incorporated into a liquid 'methylol, derivatives'iof phenols, suchiresin's 'cazilbefl'eaicted with these alkylol derivatives to yieldresinous masses which, particularly valuable .for-

the productionof.coatin'g compositions of the oil-synthetic resin type. The mixed components may be heated for a suitable time prior to dehydration in'orderto cause the'reaction to go partly or wholly to completion. or, the mixture immediately may be dehydratediin which case the substituted phenol-aliphatic aldehyde partial condensation'produ'ct and the acidic alkyd resin co-react to completion simultaneously with the dehydration ofthe r'esinousfmass.

The acidic alkyd resin is separately prepared, that is, preformed, in accordance with technique novv well known to those skilled in the alkyd resin art. Since the scope of this invention in 'volves the co-condensation of an alkylol derivativeof a substituted phenol with the alcoholic hydroxyl groups of both acidic unsaturated alkyd resins and acidic flexible alkyd resins, the composition oi the present these resins as utilized in practicing invention, is discussed briefly below.

a phenol and an aldehyde are re- AOIDIO UNSdT'URATID MIIYD RIBIN BELGIAN! In preparing the acidicunsaturated alkyd resin reactant any polyhydric alcohol containing at least two esteriflablealiphatlc hydroxyl groups,

or mixtures of such alcohols, may be used. Examples of such polyhydric alcohols areethylene gloycol, di-, triand tetraethylene glycols, propylene glycol, trimethylene glycol, thiodigiycol, glycerine, pentaerythritol, .etc. Any alpha unsaturated alpha beta polycarboxylic acid, or mixtures of such acids, may be reacted with the polyhydric alcohol or alcohols to form the unsaturated alkyd resin. Examples of such polycarboxylic acids are maleic, monohalomaleic, f-umaric,. monohalofumaric, citraconic, mesaconic, acetylene dicarboxylic, aconitic, itaconic and its homologues as, for instance, alpha methyl itaconic acid, alpha ethyl itaconic acid, alpha alpha dimethyl itaconic. acid,'etc. If available,

anhydrides of these polycarboxylic acids may be used.

In some cases, instead of using an unmodified acidic unsaturated alkyd resin I may use an unsaturated alkyd resin which has been internally modified by replacinga part, say up to about 75' The termdroxyl groups in the molecule, a non-ethylenic polycarboxylic acid containing at least three carboxyl groups in the molecule and mixtures, of

such polyhydricalcohols and. polycarboxylic acids. a

Theacidicalkyd resins oi the "flexible" and "unsaturated" types are produced by suitably reacting the components at an elevated temperature .until the acid number has'been reduced to below 210, more particularly from 40 to 210. Advantageously the components are reacted, particularly when preparing an unsaturated alkyd resin, in an inert atmosphere such asa nitrogen-atmosphere. Generally the components are reacted until fromabout55' to 93 per cent of the theoretical water of esterification has been col- "unsaturated alkyd resin? as used generally here= in and in the appended claims is intended to in-i.

clude within its meaning both unmodified esterification products of a polyhydric alcohol with an alpha unsaturated alpha beta polycarboxylic acid and esterification products of the said components which have been modified with a nonethylenic polycarboxylic acid such as above delected. Depending upon the molecular weight of the starting components, the acid number of these alkyd resins, when the ordinary reactants are used, is within the range of 40to 210. Acidic alkyd resin having an acid number higherthan 210 should not be used, since a large excess of unreactedalkyd resin components (indicated by an acid number above .210) has a detrimental efiect upon thefinished. resin and makes more dlfilcult the production of uniform batches from day today. a

The amount of acidic alkyd resin incorporated into the alkylol derivative of the substituted phenol may-bevaried over a wide range. The optimum proportion of alkyd resin to the phenolic derivative depends upon such influencing factors as, for example, the particular starting components and proportions thereof employed in producing the alkyd and phenolic resins, the

, particular-reaction time and temperatures and the particular properties desired in the end-product. Generally speaking, the alkyd resin compcnent will be not more-than '75 per cent by weightiof the dehydrated resinous mass, and in most cases. will be less than 59 per cent by weight thereof. Particularly good results have been obtained with, by weight, from 5 to 35 per cent alkyd "resin to 95 to 65 per cent phenolic resin basedon the dehydrated mass.

When a strong base in relatively large'amount is employed as a catalyst for the substituted scribed and wherein an alpha unsaturated alpha beta poiycarboxylic acid forms at least 25 mol per cent or the polycarboxylic acid reaction component. Y

Acxnrc Fmxrnta Arm Ream Rsec'rsnr Alkyd resins which are permanently flexible heretofore have been produced, one form of such resins being described and claimed in Kienleand Rohlfs Patefit'No. 1,897,260, which is assigned to the same asignee as the present invention. Flexible alkyd resins may be prepared, for example, by reacting suitable proportions of an allphatic dicarboxylic acid, e. g., succinic acid, etc., and a dihydric alcohol, e. g., ethylene glycol, etc., with the usual alkyd resin ingredients, namely a polyhydric alcohol having three or more hydroxyl groups in the molecule, e. g., glycerol, with a nonethylenic polycarboxylic acid, e. g., phthalic acid or anhydride. The term "flexible alkyd resin" as used generally hereinisintended to include within its meaning alkyd resins obtained by reaction of a dihydric alcohol or alcohols and a non-ethylenic dicarboxylic acid or acids, with or without less than mol per cent ot a reactant selected from the class consisting of polyhydric alcohols containing at least three byphenol-aliphatic aldehyde reaction, it is sometimes advantageous to use lessacidic alkyd resin than would bev required to neutralize completely the alkalinity'of the phenolic reaction product. In such cases neutralization is completed by adding a suitable amount of an organic carboxylic acid such as acetic, propionic, oxalic, malonic,

succinic, adipic, acrylic, methacrylic, polymeth-v acrylic, maleic, ,fumaric, citraconiegtartaric, cit:- ric, lactic, hydroxy malonic, etc. In thisway the amount of acidic alkydresin required for neutralization may be materially reduced.

The new synthetic resins oithis invention are soluble in, and co-reactive with drying oil, semidrying oils, and with synthetic resinous compositions internally modified by such oils, for example oil-modified glyceryl phthalate, diethylene glycol maleate, triethylene glycol maleate, tetraethylene glycolmaleate, etc. Illustrative examples of fatty oils, specifically drying and semidrying oils, which may be used in producing the liquid coating compositions (air-drying and baking varnishes) of this invention are linseed oil,

oiticica oil, China-wood oil, perilla oil, soya bean oil, etc.

To the solution of the resinous co-condensation' products of this invention may be added suitable driers and the resulting varnish used'directly as .4 ,apr otective surface coating material. Or. it

ing added to the bodied oil-resin mal's to produce a varnishctthedesired' viscosity and dry- Para phe jl phenol--.

. mately 37.1% HCHO) sired. the varnish may be bodied by heating at temperaturel'uptm'ior exam 250' to 260' C. or more, suitable driers' and volatile solvents beingrrate. Examples oi suitable driers are 'the- .metallic' naphthenates and linole'atesfior instance cobalt and manganese .naphthenates and 'linoleates, .ccbalt-maleate'lead acetate, etc. 'If

therate'oi drying is of secondary consideration,

a the drier maybeomitted; Pigments, dyesfand other conventional ingredients or varnishes may be added, ii desired. O'thernatural or synthetic film-forming materials, soluble in the oily solu-' tionsoi the resins of thisinventiomllkewise' may be employed to modify the properties of the varnish and of the dried film. These may be, for

example. cellulose derivatives suchas cellulose nitrate (pyroxylin), cellulose acetate, cellulose butyrate; certain cellulose ethers such as phenyl cellulose, benzyl cellulose, etc., polymerized butyl methacrylate, itaconicesters, particularly the to higher molecular weight members such as butyl,

amyl, hefxyl, decyl. phenyl, cresyl, etc; itaconate's, in monomeric or partially orcompletely "poly merized state. 1 7 In order that thoseskilled in the art better may understandhow. the present invention may be carried into efiect, the following examples thereof are given by way oi' illustration. All parts are by weight. j I

- Ermine 1 Preparation of resin not. The coating dried dust-tree in less than 40 minutes at room temperature. The coating composition dried to a light-colored, exceptionally -tough film after 48 'hoursdrying at room tem- 'pirature.

J Preparation of coating composition (3) I Parts China-wood oil.-.--- 10.0 Above-described resin... 4.0

Gllfcerine l 0.5 Hydrocarbon solvent 20.0

Solution of cobalt and lead drier--. 0.25

The China-wood oil, resin andglycerine were heated to 220-230 C. for 28 minutes or until an eight-inch string could be formed. The resulting mass was cooled to 150 C. and the hydrocarbon} solvent added. After cooling to below was reached. o I

Preparation of coating composit China- -woodoiL- 20.0 v, v Above-described resin 10.0 Hy'drocarbon solvent 40.0 Lead acetate -0.03

Solution of cobalt drier 0.5

182-"l90 C. for 30-45'minutes until about 67% Y of'thecalculated water oi esterification had been removed. The mixture of acidic alkyd resin and para phenyl phenol-formaldehyde partial 0ondensation product was refluxed 101125 minutes.

followed by" dehydration under a vacuum of 23 inches of mercury. During dehydration the resinous mass reached a temperature of'about 150C. 1 t

Preparation of coating composition (A) t V v vChina-wood 011-. 20.0 Above-described resin-- 10.0 Leadacetateu' 0.03 Hydrocarbon solvent .(thinner 40.0 Solution of cobalt and lead drier 0.5

The resin wasdissolvedin the China-wood oil by heating at 220" -230 C. for about 30 minutes. The hot mass was cooled to about 150 C. and the hydrocarbon solvent then added. The diluted resin solution was cooled to about 70 C..

' the drier added and the solution then filtered. 'A

base member was coated with the resulting prod- C. the'drier was added and the whole solution filtered. Upon drying the filtered varnish in film form torn hours at C. a clear, hard. tough film was obtained. vIt dried to a dust-tree condition in Iv -hours at room temperature.

Exsu'ru 2 Preparation of resin I I o P I Para tertiary amyl phenol 40.0 Aqueous solution of formaldehyde. (approximately 37.1% HCHO) 40.0 Sodium hydroxide in 10 parts water-.--- 1.2

,were refluxed for about 2 hours, yielding a mixture of methylol derivatives of para tertiary amyl' phenol. To this methylol'condensation prod-' not was added 10 parts of an-acidic ethylene glycol maleate prepared as described in Example? 1. The mixed reactants were refluxed for 'about}; l i 10 minutes, followed by dehydration un'derfa'] ff vacuum of 25.5 inches of mercury, during which, time a maximum temperature of about i00iC.

The resinwas dissolved in the China-wood oil by heating to a temperature of about 220-235' C. for about 15 minutes or until an eight-inch string could be formed. ,The drier and solvent were added as in Example 1(A) and the varnish filtered. This varnish dried to a dust-free condition in about 30 minutes at room temperature. After 48 hours during at room temperature, the varnish film color.

EXAIPLI 8 Preparation of resin 0 I Parts Para tertiary butyl phenol 18.75 Aqueous solution oi formaldehyde (approximately 37.1% HCHO) 20.0

Sodiumghydroxide in 5 to 10 parts water- 0.375

-' were mixed and refluxed for about 45 minutes,

yielding a liquid mass comprisingmainly methylol derivatives or para tertiary butyl phenol. To this liquid mass was added 5. parts of an acidic ethylene glycol maleate prepared as describedunder Example 1. The mixture was refiuxed'ior about 15 minutes, followed by dehy- Partsi f i was tough, flexible and very light in dration under a vacuum of 40 mm. of mercury. During dehydration a maximum resin temperature of about-150 C. was reached.

Preparation of coating composition Parts" China-wood nil 20.0 Above-described resin 10.0 Hydrocarbon solvent 40.0 Solution of cobalt and lead drier 0.5

The above components were mixed and bodied as described under the preceding examples. This coating composition yielded a hard, tough, flexible film after heating for 1% hours at 85 C.

EXAMPLE 4 To a methylol condensation product prepared as described under Example 3 was added5 parts of an acidic ethylene glycol itaconate of less than 210 acid number. This itaconic ester was prepared by reacting 65 parts itaconic acid and 31 parts ethylene glycol as described under Example 1 until about 80% of the calculated water of esterification had been collected. The mixed components were heated under reflux for 55 minutes, followed by dehydration as described under Example 3.

Preparation of coating composition resulting methylol condensation product was added 5 parts of an acidic ethylene glycol succinate of lessthan 210 acid number. This succinate was prepared by esterifying 62 parts ethylene glycol with 116 parts succinic acid by heating the reactants together for about 2%. hours at 195-203 C. The mixed components were refiuxed for about 45 minutes, followed by dehydration' under a vacuum of 18 inches of mercury to an internal resin temperature of 155 C. The dehydrated mass was. an oil-soluble, exceptionally light-colored resin.

' Preparation of coating composition The same components and proportions as described under Example 2 were used, with the exception that the above-described resin was em- Parts China-wood o 20.0 Above-described resin 10.0 Hydrocarbon solvent 40.0 Solution of cobalt and lead drier 0.5

were mixed and bodied as described under Example 1. A base member coated with a sample 01' this varnish yielded a clear, tough, flexible varnish film after 3 to 4 hours baking at 85-90 C.

lixzmnms 5 Preparation ojresin Parts Para phenyl phenol 21.25 Aqueous solution of formaldehyde (approximately 37.1% HCHO) 20.0 Sodium hydroxide in 10 parts water 0.49

were mixed and refluxed for 45 minutes, yielding a liquid resinous mass formed mainly of methylol derivatives of para phenyl phenol. To this liquid mass was added 5 parts of an acidic eth ylene glycol itaconate prepared as described under Example 4. The mixed components were refluxed for 15 minutes and then dehydratedat 40 mm. mercury vacuum to an internal resin temperature of about 130 C.

Preparation of coating composition Same formula as given in Example 4 with the exception that the above-described resin was emplayed as the resin component. The method of compounding the materials was essentially the same as described in Example 1. The resulting varnish yielded a clear, hard, tough film when dried for 1% hours at roomtemperature.

EXAMPLE 6 Preparation of resin Parts Paratertiary amyl phenol 20.0

Aqueous solution of formaldehyde (approximately 37.1% HCHO) 20.0 Sodium hydroxide in 4 parts water 0.6

were mixed and refluxed at the boiling temperature of the reactants for about 1 hour. To the EXAMPLE 7 I Same proportions of para phenyl phenol, aqueous formaldehyde and sodium'hydroxide and the same procedure as describedin Exampleb. To the methylol condensation product was added 5 parts of acidic ethylene glycol succinate prepared as described in Example 6. The-mixed components were refluxed for 15 minutes, after which the mass was dehydrated under a vacuum of 40 mm. mercury to an internal resin temperature of 13'? C.

' Preparation of coating composition Same components and proportions as described in Example 3 with the exception that the above resin was employed. The resin was dissolved in the oil and the mass heated at 220-230 C. for about 17 minutes or until an eight-inch string could be formed. The hydrocarbon solvent was added as thebodied varnish cooled to 150 C., followed by the addltion of the drier at a temperature below 60 C. The solution was filtered and then used in coating various metallic and wooden articles. heating for 1 hours at about C. It dried too hard, clear, flexible state after heating about 3 hours at that temperature.

EXAMPLE 8 Same component and proportions of para tertiary butyl phenol, aqueous formaldehyde and sodium hydroxide and the same procedure in preparing the methylol derivative as described in Example 3. To the methylol condensation product was added 5 parts of an acidic ethylene glycol succinate prepared as, described in Example 6. H

The mixed components were refluxed for 15 minutes, followed by dehydration at 40 mm. mercury vacuum to an internal resin temperature of Preparation of coating composition Same components and-proportions as described in Example 5 with the exception that the above resin was used. The method of compounding the The resin film driedto adust-iree state after ingredients also was feueaasn the same. as described in the. precedinsexamples. This varnish required a little lonser drying time (to reach the lame hardness) at room temperature or at elevated temperatures, for. example 85' 0., than the varnish of Example '1.

The present invention is separate and distinct from the'invention disclosed and claimed in mycopending application Serial. No. 319,518, illed concurrently herewith and assigned to the same asslgnee as the present invention. In that appli-' cation I broadly claimed a resinous reaction .product of'an alkaline-catalyzed partial condensation product of a phenol and an aliphatic aldehyde with an acidic unsaturated alkyd resin having an acid number not higher than 210. Specific claims were directed to casting resins obtained by reaction of such unsaturated alkyd resins and a partial condensation product of formaldehydewith a phenol having the graphic formula I r I on i where R is a member of thegroup consisting of hydrogen, and aryl, alkyl and alkoxy radicals What I claim as new and desire. to secure by Letters Patent of the United States is:

' 1. A composition comprising an oil-soluble. dehydrated resinous reaction product of ingredients scatters preformed unsaturated alkyd resin is a preformed acidic polyhydric alcohol itaconate having an acid number of at least 40 and not higher than 210.

7. A composition as in claim 1 wherein the preformed unsaturated alkyd resin is a preformed acidic polyhydric alcohol maleate having an acid number of at least 40 and not higher than 210.

8. A-composition as in claim 1 wherein thepreformed unsaturated alkyd resin is a preformed acidic polyhydric alcohol fumarate having an acid number of at least 40 and not higher than 210. I

9. As a new product, the oil-soluble dehydrated resinous reaction product of ingredients consisting of (l) a methylol derivative of a para-substituted amyl phenol and (2) a preformed acidic polyhydric alcohol itaconate' consisting of the incomplete reaction product of ingredients conisting of a polyhydric alcohol and itaconic acid and having an acid number of at least 40 and not higher than 210, said polyhydric alcohol itaconate constituting from 5 to 35 per cent by weight of the said dehydrated resinous reaction Product.

10. As a'new product, the oil-soluble dehydrated resinous reaction product oi ingredients consisting oi (1) a methylol derivative of aparaconsisting of 1) a preformed acidic unsaturated alkyd resin having an acid number of at least 40 and'n'ot higher than 210 obtained by incomplete reaction of ingredients consisting of polyhydric alcohol andpolycarboxylic acid, at least one such acid being essentially an alpha unsaturated alpha beta polycarboxylic acid forming at least 25 mol pericent ofthe polycarboxylic acid, and- (2) a liquid alkaline-catalyzed partial condensation product of ingredients consisting of formaldehyde and a substituted phenol .selected from the class consisting of ortho-substituted and parasubstituted phenols having two reactive positions in the: aromatic :nucleus and containing 7 at east four, carbon atoms in the substituent grcupins. said alkyd resin constitutingi'rom5 to 50 per cent by weight of the-said dehydrated resinous reaction product.' y g 2. As a new product. the oll-soluble'dehydrated resinous reactioniproduct' oi ingredients consisting or 1) a preformed acidic unsaturated allwd resin having an acidnurnber of at least 40 and 'not higher than2l0. obtainedby'incomplete reaction of ingredients consisting' vof a .polyhydric alcohol and an alpha unsaturated alpha beta polycarboxylic'acid" and (2) a methylol derivative of a substituted phenol selected from the class cons sting of'ortho-substituted and parasubstituted phenols having two reactive positions in the aromatic nucleus and containing at least four carbon-atoms in the substituent grouping,

saidalkyd resin constituting from 5 to 50'per.

cent by weight of the said dehydrated resinous reaction product; I

a 3. A product as in claim 2 wherein the substituted phenol isa para-substituted amyl phenol. 4. A product as in claim 2 wherein the substituted phenol is a para-substituted indene phenol. 5. A productas in claim 2 wherein the substituted phenolis a para-substituted l-phenethyl phenol."

6. A composition as in claim 1 wherein the substituted indene phenol and (2) a preformedacidic polyhydric alcohol maleate consisting of the incomplete reaction product of ingredients consisting of a polyhydric. alcohol and maleic acid and having an acid number of at least 40 and not higher than 210, said polyhydric alcohol maleate' constituting from 5 to 35 per cent by weight of the said dehydrated resinous reaction product.

11. As a new product, the oil-soluble dehydrated resinous reaction product of ingredients consisting of (1) a methylol derivative of a parasubstituted l-phenethyl phenol and (2) a preformed polyhydric alcohol fumarate consisting oi the incomplete reaction product of ingredients consisting of a polyhydric alcohol and furnaric acid and having an acid number 01' at least 40 and not higher than 210,. said polyhydric alcohol fumarate constituting from 5 to 35 per cent by vweight of the said dehydrated resinous reaction ing at least 25 mol per cent of the polycarboxylic acid component, and (2) a liquid alkaline-catalyzed partial condensation product of ingredients consisting of formaldehyde and a substituted phenol selected from the class consisting of ortho-substituted and para-substituted phenols having two reactive positions in the aromatic nucleus and containing at least four carbon atoms in the substituent grouping, said alkyd resin constituting from 5 to 35 per cent by weight of the I said dehydrated resinous reaction product.

14. The method which comprises effecting reaction at a temperature not exceeding substantially C. between ingredients consisting of solution of from 1 to 5 mols formof a substituted phenol sean aqueous aldehyde and 1 mol lected from the class consisting of ortho-substituted and para-substituted phenols having two reactive positions in the aromatic nucleus and containing at least four carbon atoms in the ubstituent grouping, said reaction being carried out in the presence of an alkaline catalyst for a period suflicient to form. a liquid mass comprising a methylol derivative of the said phenol, reacting with the said liquid mass a preformed acidic unsaturated alkyd resin having an acid number or at least 40 and not higher than 210 obtained by incomplete reaction of ingredients consisting oi! pclyhydric alcohol and polycarboxylic acid, at least one such acid being essentially an alpha unsaturated alpha beta polycarboxylic acid forming at least 25 mol per cent of the polycarboxylic acid, and the amount of the said alkyd resin being such that it constitutes from 5 to 35 per cent by weight of the dehydrated mass, and dehydrating the resulting reaction product under reduced pressura'the dehydrated product being characterized byits solubility in fatty oils.

GAETANO F. DALELIQ. 

